US6028047A - Use of formamidinium salts as bleach activators - Google Patents
Use of formamidinium salts as bleach activators Download PDFInfo
- Publication number
- US6028047A US6028047A US09/229,204 US22920499A US6028047A US 6028047 A US6028047 A US 6028047A US 22920499 A US22920499 A US 22920499A US 6028047 A US6028047 A US 6028047A
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- United States
- Prior art keywords
- detergent
- cleaner
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- alkyl
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/3927—Quarternary ammonium compounds
Definitions
- This invention relates to the use of formamidinium salts as bleach activators and to detergent compositions comprising these compounds as bleach activators.
- peroxidic bleaches such as perborates, percarbonates, persilicates and perphosphates
- bleach activators adding the precursors of bleaching peroxy acids, which are often referred to as bleach activators.
- bleach activators are usually reactive organic compounds containing a O-acyl or N-acyl group which, in alkaline solution together with a source of hydrogen peroxide, form the corresponding peroxy acids.
- bleach activators are, for example, N,N,N,N-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucolurile (TAGU), tetraacetylcyanic acid (TACA), di-N-acetyldimethoxyglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).
- TAED N,N,N,N-tetraacetylethylenediamine
- GPA glucose pentaacetate
- TAX xylose tetraacetate
- SBOBS sodium 4-benzoyloxybenzenesulfonate
- STHOBS sodium trimethylhexanoyloxybenz
- bleach activators are amidines and salts derived therefrom, of the formula ##STR2## where Y is a halogen atom, and HA is an inorganic or organic acid.
- Y is a halogen atom
- HA is an inorganic or organic acid.
- the invention provides for the use of formamidinium salts of the formula ##STR3## as bleach activators, where R 1 , R 2 , R 3 and R 4 independently of one another are C 1 -C 24 -alkyl, C 2 -C 24 -alkenyl, C 1 -C 24 -hydroxyalkyl, C 2 -C 24 -chloroalkyl, C 1 -C 24 -aminoalkyl, aryl, C 1 -C 4 -alkylaryl or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl,
- R 1 and R 2 and/or R 3 and R 4 together with the nitrogen atom to which they are bonded
- R 1 , R 2 , R 3 and R 4 independently of one another are C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, phenyl, or R 1 and R 2 and/or R 3 and R 4 together with the nitrogen atom to which they are bonded, form a five-, six- or seven-membered ring, or R 1 and R 3 or R 2 and R 4 together with the nitrogen atom to which they are bonded and the carbon atom between these nitrogen atoms form a five-, six- or seven-membered ring.
- Suitable anions A are chloride, bromide, iodide, fluoride, sulfate, hydrogensulfate, carbonate, hydrogencarbonate, phosphate, monohydrogenphosphate and dihydrogenphosphate, pyrophosphate, metaphosphate, hexafluorophosphate, nitrate, methosulfate, dodecylsulfate, dodecylbenzenesulfonate, tosylate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonate, formate, acetate or propionate.
- the formamidinium salts are readily available by a simple route by reacting urea derivatives with suitable halogenating agents, such as, for example, phosgene, oxalyl chloride, phosphorus pentachloride and trichloride, phosphorus oxychloride, and the corresponding bromides; such reactions are described, for example, in A. Marhold "Kohlensaurederivate” [Carbonic acid derivatives], Methoden der Organischen Chemie [Methods in organic chemistry] (Houben-Weyl), H. Hagemann (ed.), Vol. E 4 (1983), p. 671-677 and the literature cited therein.
- suitable halogenating agents such as, for example, phosgene, oxalyl chloride, phosphorus pentachloride and trichloride, phosphorus oxychloride, and the corresponding bromides; such reactions are described, for example, in A. Marhold "Kohlensaurede
- the invention also provides bleaching detergents and cleaners containing formamidinium salts as defined above.
- these detergents and cleaners usually also comprise surface-active compounds and other ingredients.
- Suitable peroxy compounds are alkali metal peroxides, organic peroxides, such as urea peroxide, and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Mixtures of two or more of these compounds are also suitable. Particular preference is given to sodium perborate tetrahydrate and, in particular, sodium perborate monohydrate.
- sodium perborate monohydrate Due to its long shelf life and its good solubility in water, sodium perborate monohydrate is preferred. Sodium percarbonate may be preferred because of environment-protection reasons.
- Alkali hydroperoxides are another suitable group of peroxy compounds. Examples of these substances are cumene hydroperoxide and t-butyl hydroperoxide.
- Such detergents and cleaners can comprise the bleach activator according to the invention in an amount by weight of from about 0.05 to 20%, preferably from 0.5 to 10%, in particular from 1 to 7.5%, together with a peroxy compound.
- the amount by weight of these peroxy compounds is usually from 1% to 60%, preferably from 4 to 30%, in particular from 10 to 25%.
- the detergent and cleaners may also comprise other suitable bleach activators, such as, for example, TAED, tetraacetylglycolurile, glucose pentaacetate, sodium nonanoyloxybenzenesulfonate, benzenecaprolactam or nitrilic activators in an amount of from 1 to 10% by weight.
- suitable bleach activators such as, for example, TAED, tetraacetylglycolurile, glucose pentaacetate, sodium nonanoyloxybenzenesulfonate, benzenecaprolactam or nitrilic activators in an amount of from 1 to 10% by weight.
- the surface-active compounds can be derived from natural products, such as, for example, soaps, or are a synthetic compound from the group consisting of anionic, nonionic, amphoteric, zwitterionic or cationic surface-active substances, or mixtures thereof. Many suitable substances are available commercially, and are described in the literature, for example in "Surface active agents and detergents", Vol. 1 and 2, by Schwartz, Perry and Berch.
- a total amount of surface-active compounds can be up to 50% by weight, preferably from 1% by weight to 40% by weight, in particular from 4% by weight to 25% by weight.
- Suitable synthetic anionic surface-active substances are alkali metal salts of organic sulfates and sulfonates containing alkyl radicals having from about 8 to 22 carbon atoms, the term "alkyl” including the alkyl substituents of higher aryl radicals.
- sulfates and sulfonates are sodium and ammonium alkylsulfates, specifically the sulfates obtained by sulfation of higher (C 8 to C 18 ) alcohols; sodium and ammonium alkylbenzenesulfonates containing alkyl radicals from C 9 to C 20 , in particular linear secondary sodium alkylbenzenesulfonates containing an alkyl radical from C 10 to C 15 ; sodium alkylglyceryl ether sulfates, particularly the esters of higher alcohols derived from taro oil and coconut oil; the sodium sulfates and sodium sulfonates of coconut fatty acid monoglycerides, sodium and ammonium salts of the sulfuric esters of higher (C 9 to C 18 ) oxalkylated fatty alcohols, in particular those oxalkylated with ethylene oxide; the reaction products of the esterification of fatty acids with isethionic acid and subsequent neutralization with sodium hydrox
- nonionic surface-active compounds which are preferably used together with anionic surface-active compounds, are, in particular, the reaction products of alkylene oxides (usually ethylene oxide) with alkylphenols (alkyl radicals from C 5 to C 22 ), the reaction products generally containing from 5 to 25 ethylene oxide (EO) units in the molecule, the reaction products or aliphatic (C 8 -C 18 ) primary or secondary, linear or branched alcohols with ethylene oxide, containing, in general, from 6 to 30 EO, and the addition products of ethylene oxide with reaction products of propylene oxide and ethylenediamine.
- Other nonionic surface-active compounds are alkyl polyglycosides, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulfoxides.
- Amphoteric or zwitterionic surface-active compounds can also be used in the compositions according to the invention, although ir most cases this is not preferable due to their high costs. If amphoteric or zwitterionic compounds are used, then it is generally in small amounts in compositions which principally comprise anionic and nonionic surfactants.
- soaps in the compositions according to the invention preferably in an amount of less 25% by weight. They are particularly suitable in small amounts in binary (soap/anionic surfactant) or in ternary mixtures together with nonionic or mixed synthetic anionic and nonionic surfactants.
- the soaps used are preferably the sodium salts, and less preferably the potassium salts, of saturated or unsaturated C 10 -C 24 fatty acids or mixtures thereof.
- the amounts of such soaps can be from 0.5 to 25% by weight, lower amounts of from 0.5 to 5% by weight generally sufficing for foam control. Soap contents between 2 and about 20%, particularly between about 5 and about 10%, have a positive effect. This is the case particularly in hard water, where the soap serves as an additional builder substance.
- the detergents and cleaners generally also comprise a builder.
- Suitable builders are: calcium-binding substances, precipitants, calcium-specific ion exchangers and mixtures thereof.
- Examples of calcium-binding substances include alkali metal polyphosphates, such as sodium polyphosphate, nitrilotriacetic acid and its water-soluble salts, the alkali metal salts of carboxymethoxysuccinic acid, ethylenediaminetetraacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, citric acid and polyacetal carboxylates, as disclosed in U.S. Pat. No. 4,144,226 and U.S. Pat. No. 4,146,495.
- precipitants are sodium orthophosphate, sodium carbonate and soaps of long-chain fatty acids.
- ion exchangers which are specific for calcium are the various types of water-insoluble, crystalline or amorphous aluminum silicates, of which the zeolites are the best-known examples.
- These builder substances can be present in amounts of from 5 to 80% by weight, an amount of from 10 to 60% by weight being preferable.
- the detergents and cleaners may comprise any of the conventional additives in amounts which are usually found in such compositions.
- these additives include foam formers, such as, for example, alkanolamides, particularly the monoethanolamides from palm kernel oil fatty acids and coconut fatty acids, antifoams, such as, for example, alkyl phosphates and alkylsilicones, antiredeposition agents and similar auxiliaries, such as, for example, sodium carboxymethylcellulose and alkyl or substituted alkyl cellulose ethers, stabilizers, such as ethylenediaminetetraacetic acid, softeners for textiles, inorganic salts, such as sodium sulfate, and, in customarily small amounts, fluorescent substances, perfumes, enzymes, such as proteases, cellulases, lipases and amylases, disinfectants and dyes.
- the bleach activators of this invention can be used in a large number of products. These include textile detergents, textile bleaches, surface
- the bleach activators in the form of granules which, in addition to the bleach activator, comprise a binder.
- granules which, in addition to the bleach activator, comprise a binder.
- Various methods of producing such granules are described in the patent literature, for example in CA-1 102 966, GB-1 561 33, U.S. Pat. No. 4,087,369, EP-A-0 240 057, EP-A-0 241 962, EP-A-0 101 634 and EP-A-0 062 523. Any of these methods can be used for the bleach activators according to the invention.
- the granules comprising the bleach activators are generally added to the detergent composition together with other, dry constituents, such as, for example, enzymes or inorganic peroxide bleaches.
- the detergent composition to which the activator granules are added can be obtained in various ways, such as, for example, by dry mixing, extruding and spray drying.
- the bleach activators according to the invention are particularly suitable for nonaqueous liquid detergents, together with a bleaching peroxy compound, for example sodium perborate, for giving the detergent a high level of detergency for fabrics and textiles.
- a bleaching peroxy compound for example sodium perborate
- Such nonaqueous, liquid detergents which include pasty and gelatinous detergent compositions, are known in the prior art, and are described, for example, in U.S. Pat. No. 2,864,770, U.S. Pat. No. 2,940,938, U.S. Pat. No. 4,772,412, U.S. Pat. No.
- compositions are in the form of a nonaqueous, liquid medium in which a solid phase can be dispersed.
- the nonaqueous, liquid medium can be a liquid surface-active substance, preferably a nonionic surface-active substance, a non-polar liquid medium, such as, for example, liquid paraffin, a polar solvent, such as, for example, polyols, for example, glycerol, sorbitol, ethylene glycol, possibly in combination with low molecular weight monohydric alcohols such as ethanol or isopropanol, or mixtures thereof.
- the solid phase can consist of builder substances, alkalis, abrasive substances, polymers, other solid ionic surface-active substances, bleaches, fluorescent substances and other customary solid ingredients.
- the bleaching action was then quantified by determining the differences ⁇ R.sub.(ACT) in the reflectances before and after bleaching using an ELREPHO 2000 whiteness measuring device (Datacolor). These ⁇ R.sub.(ACT) values and the ⁇ R O values determined in the control experiments without bleach activator were used to calculate the ⁇ R values listed in Table 1, which are a direct measure of the improvement in bleaching action caused by the addition of activator:
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19801049 | 1998-01-14 | ||
DE19801049A DE19801049A1 (de) | 1998-01-14 | 1998-01-14 | Verwendung von Formamidinium-Salzen als Bleichaktivatoren |
Publications (1)
Publication Number | Publication Date |
---|---|
US6028047A true US6028047A (en) | 2000-02-22 |
Family
ID=7854523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/229,204 Expired - Fee Related US6028047A (en) | 1998-01-14 | 1999-01-13 | Use of formamidinium salts as bleach activators |
Country Status (4)
Country | Link |
---|---|
US (1) | US6028047A (fr) |
EP (1) | EP0930358B1 (fr) |
JP (1) | JPH11256188A (fr) |
DE (2) | DE19801049A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090176805A1 (en) * | 2007-11-27 | 2009-07-09 | Cronyn Marshall W | Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7700533B2 (en) | 2005-06-23 | 2010-04-20 | Air Products And Chemicals, Inc. | Composition for removal of residue comprising cationic salts and methods using same |
DE102006018345A1 (de) * | 2006-04-19 | 2007-10-25 | Henkel Kgaa | Aufhell- und/oder Färbemittel mit Amidinen |
WO2011019189A2 (fr) * | 2009-08-11 | 2011-02-17 | 동우 화인켐 주식회사 | Composition pour solution darrachage dun enduit protecteur et procédé darrachage denduit protecteur lutilisant |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB836988A (en) * | 1955-07-27 | 1960-06-09 | Unilever Ltd | Improvements in or relating to bleaching and detergent compositions |
GB907356A (en) * | 1959-06-19 | 1962-10-03 | Konink Ind Mij Voorheen Noury | Improvements in or relating to washing and/or bleaching compositions |
EP0098129A1 (fr) * | 1982-06-30 | 1984-01-11 | The Procter & Gamble Company | Additif de produit détergent |
US4451384A (en) * | 1980-10-24 | 1984-05-29 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Haloformamidines bleaching agent activator functioning to release active oxygen |
EP0120591B1 (fr) * | 1983-02-23 | 1987-09-23 | The Procter & Gamble Company | Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage |
US5549715A (en) * | 1993-11-23 | 1996-08-27 | Degussa Austria Gmbh | Method for bleaching textile material |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5686015A (en) * | 1994-08-31 | 1997-11-11 | The Procter & Gamble Company | Quaternary substituted bleach activators |
US5584888A (en) * | 1994-08-31 | 1996-12-17 | Miracle; Gregory S. | Perhydrolysis-selective bleach activators |
US5460747A (en) * | 1994-08-31 | 1995-10-24 | The Procter & Gamble Co. | Multiple-substituted bleach activators |
-
1998
- 1998-01-14 DE DE19801049A patent/DE19801049A1/de not_active Withdrawn
-
1999
- 1999-01-02 EP EP99100003A patent/EP0930358B1/fr not_active Expired - Lifetime
- 1999-01-02 DE DE59909070T patent/DE59909070D1/de not_active Expired - Fee Related
- 1999-01-13 US US09/229,204 patent/US6028047A/en not_active Expired - Fee Related
- 1999-01-13 JP JP11006573A patent/JPH11256188A/ja not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB836988A (en) * | 1955-07-27 | 1960-06-09 | Unilever Ltd | Improvements in or relating to bleaching and detergent compositions |
GB907356A (en) * | 1959-06-19 | 1962-10-03 | Konink Ind Mij Voorheen Noury | Improvements in or relating to washing and/or bleaching compositions |
US4451384A (en) * | 1980-10-24 | 1984-05-29 | L'air Liquide - Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Haloformamidines bleaching agent activator functioning to release active oxygen |
EP0098129A1 (fr) * | 1982-06-30 | 1984-01-11 | The Procter & Gamble Company | Additif de produit détergent |
EP0120591B1 (fr) * | 1983-02-23 | 1987-09-23 | The Procter & Gamble Company | Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage |
US5549715A (en) * | 1993-11-23 | 1996-08-27 | Degussa Austria Gmbh | Method for bleaching textile material |
Non-Patent Citations (2)
Title |
---|
Houben Weyl, Bd. E4 (1983), S. 671 677. * |
Houben-Weyl, Bd. E4 (1983), S. 671-677. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090176805A1 (en) * | 2007-11-27 | 2009-07-09 | Cronyn Marshall W | Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents |
US8124793B2 (en) | 2007-11-27 | 2012-02-28 | Gail Marie Cronyn, legal representative | Derivatives of ethylene methanedisulfonate as cancer chemotherapeutic agents |
Also Published As
Publication number | Publication date |
---|---|
EP0930358A3 (fr) | 1999-11-17 |
JPH11256188A (ja) | 1999-09-21 |
EP0930358B1 (fr) | 2004-04-07 |
DE59909070D1 (de) | 2004-05-13 |
DE19801049A1 (de) | 1999-07-15 |
EP0930358A2 (fr) | 1999-07-21 |
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Owner name: CLARIANT GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:NESTLER, BERND;REEL/FRAME:009701/0254 Effective date: 19990105 |
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Effective date: 20040222 |
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STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |